Process for printing textiles and printing preparations therefor



PROCESS son PRINTING TEXTILES AND PRINTING PREPARATIQNS THEREFOR EduardMoser, Basel, and Albert Bolleter, Muttenz, Switzerland, assignors toCiba Limited, Basel, Switzerland, I

No Drawing. Application October 7, 1957 Serial No. 688,398

I Claims priority, application Switzerland October 18, 1956 1 Claim.(Cl.8-71) The present invention is based on the observation thatvaluable prints on textiles can be produced by-printing on the textile acoupling component and a stabilized diazo-compound followed bydevelopment of the dyestufr under neutral conditions such as by steamingwith neutral steam, if there is used a printing preparation whichcontains as coupling component a 4-arylazo-l-amino-7- hydroxynaphthalenefree from groups imparting solubility in water and as stabilizeddiazo-compound a diazoamino-compound of the formula in which Rrepresents an at most bicyclic aryl radical-'7 free from groupsimparting solubility in water, X repre- Patent sents a hydrocarbonradical which may contain a group imparting solubility in water, and Yrepresents a hydrogen atom or a sulfonic acid group.

As examples of 4-arylazo-l-amino-7-hydroxynaphthalenes there bay bementioned, for example, 4-a'-naphthylazo-l-amino-7-hydroxynaphthalene,and especially 4- arylazo-l-amino-7-hydroxynaphthalenes of the formulaN=NR1 in which R represents a napthalene radical which may besubstituted or advantageously a benzene radical. The

coupling components of the Formula 2 can be made by methods inthemselves known, for example, by coupling 1-amino-7-hydroxynaphthalenein a strong to weakly acid medium with a diazotized aminonaphthalene oraminobenzene derivative, such as Patented Apr. 5, 1960 Z-methylorZ-methoxy-l-aminobenzene-5-sulfonic acid amides, such asZ-methyl-l-aminobenzene-S-sulfonic acid diethylamide.

The diazoamino-compounds to be used with the aforesaid couplingcomponents for making the printing preparations to be used in theprocess of this invention can be obtained by methods in themselvesknown, for example, by condensing a diazotized at most bicyclic aromaticbase, which isfree from groups imparting solubility in water, with anaminobenzene carboxylic acido'f the formula E O X l OOOH in which Yrepresents a hydrogen atom or a sulfonic acid group, and X represents ahydrocarbon radical which may contain a group imparting solubility inwater, especially a carboxylic acid group. As such hydrocarbon radicalsthere may be mentioned, for example, methyl, ethyl, propyl, benzyl,isopropyl and isobutyl groups, and also the radicals of carboxylicacids, for example, the radical CH CH COOH or As examples of compoundsof the Formula 3 there may be mentioned:

1-methylaminobenzene-Z-carboxylic acid-4-sulfonic acid,1-benzylaminobenzene-Z-carboxylic acid-4-sulfonic acid,1-ethylaminobenzene-Z-carboxylic acid-4-sulfonic acid,1-isopropy1aminobenzene-Z-carboxylic acid 4-sulfonic acid,1-butylaminobenzene-2-carboxylic acid-4-sulfonic acid,-1-isobutylaminobenzene-Z-carboxylic acid-4-sulfonic acid,a-(2-carboxyphenylamino) -propionic acid,a-(Z-carboxyphenylamino)-butyric acid, a-(2-carboxyphenylamino)-valericacid, a-(2-carboxyphenylamino)-B-methylbutyric acid andu-(2-carboxyphenylamino)-phenyl-acetic acid.

As diazo-compounds to be condensedwith the aforesaid compounds of theFormula 3 there may be mentioned, for example, the diazo-compoundsobtainable by ,methods in themselves known from the following aromaticbases: I ii-Naphthylamine and especially 2:5-dichloroaniline,2:5-dimethoxyor Z-methyl-S-chloraniline,

, Z-methoxyor 2-methyl-4-nitroaniline, v i

2: 5 -dimethoxy-4-benzoylaminol-aminobenzene, 2 5 -diethoxy-4-benzoylaminol-aminob enzene, Z-methoxy5-methyl-4-benzoylamino-l-aminobenzene, l-aminobenzene-3-sulfonic acidpiperidide, 1-amino-2-methoxybenzene-S-sulfonic acid diethylamide,1-amino-2-methylbenzene-5-sulfonic acid diethylamide,lamino-2-methylbenzene-5-sulfonic acid dimethylamide,1-arnino-2-methylbenzene-S-sulfonic acid morpholidegl-amino-Z-rnethylor-methoxybenzene 5sulfonic acid piperidide.

The condensation is advantageously carried out in an alkaline medium,and the-alkali metal salts of the diazoamino-compounds so obtained caneasily be .isolatedby 7 methods in themselves known, for example, bysaltingout or by subjecting solutions thereof, it desired, atterfiltering them, to a rapid drying operation;

The printing preparations are prepared fi'om" the aforesaid componentswith the solvents and thickening agents usual ,for such preparations.Advantageous'ly,-there .ai'e

used-inthe process of this invention printing preparati6i1 of theaforesaid kind, which contain free alkali metal hydroxide, for example,sodium hydroxide or potassium hydroxide.

" By the process of this invention fabrics ormixed methods white orcolored reserves can be produced on materials dyed in the mannerdescribed above.

In many cases the printing yield can be somewhat improved if, beforedrying, the printed material is treated be used for padding fabrics ormixed fabrics, especially those of cellulose fibers, by the customarymethods, for

then dried at 50-60 C. and, as described above for 'f printing,subsequently developed, by neutral or acid steaming or by dry heattreatment at a temperature above 100' C.

fabrics, especially those of cellulose fibers, are printed for -60seconds in a bath, especially an acid bath,

by known methods, for example, by screen printing or containingbichromate, for example in a bath containing roller printing. Strongprints are obtained by steaming per liter, 2 grams of sodium bichromateand 3-5 grams with neutral steam and also in most cases by steaming ofacetic acid of strength. This treatment is espe with acid steam. In manycases the printed fabrics, cially advantageous when the printing pastehas been which have been dried in the usual manner, can also 10 allowedto stand for quite some time. 7

'be developed by heating them at a temperature above The followingexamples illustrate the invention, the 100 C., and advantageously130-150" C. This heating parts and percentages being by weight:

may be carried out, for example, in chambers heated Exam le 1electrically or by other means, and without supplying p steam. For thispurpose a small proportion of a hydro- 15 In this example there are usedthe following printing philic substance, for example, glycerine must beadded colors of which 100 parts have the following composito theprinting paste. tions:

Diazoamino-cornpormd obtained from- Sodium Tint oi Titre, Parts CouplingComponent Parts Sodium dilsopronylprint so percent sulfate obtained IBase Stabiliser sulionate A 1 Amino 2 mcthoxy 1 isobutylamino ben- 6064.0 1:7-aminonaphthol-4:1'- 27. 8 7.2 1. 0 dark olive.

4-nltrobenzene. zene-2-carb0xylicacidazo 2 methoxy 5 4-su1fonic acid.chlorobenzene. 13 do 60 62. 0 1:7-aminonaphthol-4:1- 27. 3 9. 7 1. 0reddish az0-2:5'-d1chlorobenblack. zene.

C 1-Amino-2-mcthoxy-. 1-ethylaminobenzene-2- 60 58.51:7-amin0naphthol-4:1'- 28.7 11.8 1.0 black.

5-chlorobenzene. carboxylic acid-tsulazo 2 methoxy 4 nic acid.nltrobenzene.

D 1 Amino 2- methyl :1 (2 carboxyphenyl) 67.2 do 28.4 3.4 1.0 brownish4-nitrobenzene. aminovaleric acid. black.

E l-Amino-z-methoxyl-Isobutylaminobcnzene- 58 65.5 do 23.2 10.3 1.0black.

benzene 5 sulionic 2 carboxylic acid-4- acid morpholide. suli'onic acid.

F 1 Amino 2 methyl 1 isopropylamlnoben 63 62. 1 1:7-aminonaphthoi-4:1'-23.8 13. 1 1.0 grey benzene 5 sulionic zene 2 carboxylic azo 2 methly 4brown. acid dlethylamlde. acid 4 sulionic acid. chlorobenzene.

G 1 -Amino -2 -mcthoxy 1 ethylaminobenzene 60 60. 61:7-aminonaphthol-4:1'- 28. 4 10.0 1.0 brownish 5-chlorobcnzene. 2carboxylic acid 4 azo 2 methyl 4 black.

sultonlc acid. nitrobenzene. H 1-amino-2-methyl-5- ..--.do 62.91:7-am1nonaphthol-4:1- 29.8 6.3 1.0 olive chlorobcnzene. azo 2 methoxy 4brown.

chloro 5 methylbenzone. I 1-Am1no-2-meth0xy- .-.--d0 58.01:7-aminonaphthol-4:1- 29.6 11.4 1.0 black. fi-chlorobenzene. azo 2:5dimethoxy 4'-nitrohenzene.

K 1 Amino 2 methyl a (2 carboxyphenyl) 50 67. 5 1:7-aminonaphtho1-4:1'-26. 4 5. 1 1. 0 dark d-nltrobenzene. aminovaleric acid. azo 2' methyl 4'brown.

chlorobenzene.

L 1-Amin0-2:5dich1orobcna (2 carboxyphenyl) 48 69. 71:7-ami11onaphth0l-4:1'- 26.9 2. 4 1. 0 brown.

- zene; aminophenylaceticacid. azo-2:4'-din1trobenzene.

M 1 Amino 2 chloro 5 a (2 carboxyphenyl) 48 67. 2 1:7-amlnonaphthol-4:1-25. 0 6.8 1.0 violet trlfluoromethylbenzene. nmilo-mmethylbutyric azo-2'-nitro-4-chlorobrown.

i aci enzene.

N 1 Amino 2 methoxy 1 ethylaminobenzene 60 63.0 1:7-aminonaphtho1-41:-28. 6 7. 4 1. 0 brownish 5chlorobenzene. 2-carboxyllc ac1d-4-azo-naphthalene. black.

. Y snlionic acid.

0 1 Amino 2 methyl -.---do 82 45.9 1:7-aminonaphthol-4:2'- 25.9 27.2 1.0 olive benzene 5 sulionlc azo-6-methoxynaphbrown.

acid-dlcthylamide. thalene.

Solutions obtained by replacing by water -100,% With the above printingcolors there are prepared of the thickening agent present in a printingpaste can printing pastes having the following compositions:

A B C D E F G H J K L M N 0 Printing color .Q--- 100 120. 100 120 120120 120 120 120 120 120 120 120 Alcohol (denatured)- 50 80 80 60 60 8060 50 80 60 60 60 80 80 Turkey Red nil 40 40 40 40 40 40 Urea 30 30 5030 30 50 50 50 30 30 30 30 30 Water 325 270 280 255 255 250 230 295 250250 250 250 270 285 Neutral Starchtragac 450 450 450 450 450 450 450 530450 450 450 450 450 450 Sodium chlorate (solid) 10 10 10 10 10 10 10 1010 10 10 10 10 Turpentine 011 10 10 10 10 10 10 10 10 10 10 10 10 10 10A cotton fabric is printed with the above printing pastes. The printedfabric is then dried at 50-60 C., and

example, on a 2-roller foulard. The dyed fabrics are 70 steamed neutralin a Mather-Flatt steamer for 5-8 minutes at C. The fabric is rinsed inthe cold, and treated for 10 minutes at 40-50 C. with an enzymepreparation in order to remove the starch. It is again rinsed in thecold, soaped at the boil for 10minutes," and By using the customarypreprinting or over-printing 75 dried after being rinsed again. Thereare obtained ruu Alcohol (denatured) means-es pure prints. The sameprinting yield can generally be obtained by means of dry heat, forexample, when the fabric, which has been printed and predried in theusual manner, is developed by heating it at a temperature above 100 C.,advantageously within the range of 130 C. to 150 C., or by acid steamingfor 25 minutes at 100 C., instead of neutral steaming. In many cases theprinting yield can be somewhat improved by treating the printed materialbefore it is dried for 30-60 seconds in a bath at 40 C. which contains,per liter, 2 grams of sodium bichrornate and 3-5 grams of acetic acid of40% strength.

The diazo-amino-compound used for preparing the printing paste F may beprepared as follows:

24.2 parts of 1 amino-2meth ,'lbenzene-5-sulfonic acid diethylamide arediazotized in the usual manner in 45 parts of hydrochloric acid of;10%strength and 30 parts of ice with 6.9 parts of sodiumnitrite in 25parts'of water.

At the same time 28.5 parts of l-isopropylarnino benzene-2-carboxylicacid-4-sulfonic acid are dissolved in 200 parts of water with theequivalent quantity of sodium hydroxide solution of 30% strength, and 60parts of potassium carbonate are added. When dissolution is com plete,the whole is cooled to C., and the filtered diazosolution is introduceddropwise in the course of 20 minutes while stirring well. After a shorttime the diazoamino-compound crystallizes out in fine lamellae and after2 hours the coupling is complete. In order to complete the precipitationof the product 10 volumes percent of sodium chloride are added, thewhole is stirred for a further hour, and then the well crystallizedprecipitate is filtered off with suction. It is washed with a smallamount of saturated sodium chloride solution, pressed and dried in vacuoat 45-50 C.

The diazoamino-cornpound is obtained in good yield and has a content of65-70% and is easily soluble in water.

The diazoamino-compound used for making the printing preparation E isobtained as follows:

A diazo-solution prepared in the usual manner from 27.2 parts of1-amino-2-methoxybenzene-S-sulfonic acid morpholide of the formulaCHr-GH:

N- OaS OCH;

GEM-C 2 the end the mixture is adjusted to apH value of 10, filtered toremove a small amount of impurities and the solution is evaporated in aspray drier in which the inlet temperature of the air is between 130 and180 C., and the outlet temperature is not less than 70 C. and notsubstantially higher than 100 C.

The fine yellowish powder so obtained has a content of about 50% ofdiazo-amino-compound. .The yield amounts to 80 to 85% of the theoreticalyield.

Example 2 A solution is prepared having the following composition:

Parts Printing color C of Example 1 100 80 50 Urea Sodium hydroxidesolution of 30% strength Neutral tragacanth thickening (8021000) 100"Water g Azcotton fabric is padded with, the above solutionon a Z-rollerfoulard, and then squeezed and dried .at 50-60. C. It is then steamedneutral for 5-8 minutes in. a. Mather-Flatt steamer, rinsed in the cold,soaped at the boil for minutes, again rinsed, and dried. There isobtained a full level black dyeing.

The same dyeing can also be produced by acid steaming for 2-5 minutes,instead of neutral steaming, or by heating the fabric for 5 minutes inan electrically heated chamber at 150 C. 7

Example 3 A white reserve can be produced vby preprinting on a fabricdyed in accordance with Example 2, in the following manner:

A cotton fabric printed with a'printing paste consisting of 10 parts 130parts 20 parts 200 parts 40 parts 1000 parts The fabric is dried at50-60 C. and then foularded with a solution of printing colorC asdescribed in Example 2. By the further treatment described in thatexample there is obtained a pure white efiect on a black ground.

Example 4 The following printing pastes are printed side by side on acotton fabric which has been padded as described in Example 2 and dried:

150 parts of Ciba Scarlet G double extra paste (Color Index, 2ndedition, 1956, vol. II, page 2475, v No. 73860) are stirred into 700parts of a thickening of the composition given below, and then 7 partsof sodium formaldehyde-sulfoxylate and 60 parts of water are added 01000 parts 7 90 parts of Cibanone Brilliant Green BF paste conc. (ColorIndex, 2nd edition, 1956, vol. 11, page 2519, No. 59825) are stirredinto 800 parts of a thickening of the composition given below, and then80 parts of sodium formaldehyde-sulfoxylate and 30 parts of water areadded The thickening used in printing pastes (a) and (b) is preparedfrom 1000 parts The printed fabric is dried at 5060 C., and then steamedneutral in a Mather-Flatt steamer for 5-8 minutes at C. The material isthen rinsed in the cold, treated with an enzyme preparation for 10minutes at in which X represents a member selected from the groupconsisting of H and OCH and the labile diazoamino compound which in itsfree acid state corresponds to the formula References Cited in the fileof this patent UNITED STATES PATENTS Morschel Nov. 1, 1938 Moser Feb.12, 1957 COOH SOzH

